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Final Exam Organic Chemistry 2301-1

Spring 2006 Wednesday, May 10, 2006 13 pages. Please write down your name on the Front Page, and last name on all pages. You may NOT use any notes or textbooks. You can use molecular models during the exam. Raise your hand if you have a question. Exam begins at 10:30 am and ends at 12:30 pm. Everyone is asked to remain seated until the end of the exam to minimize disturbance of students finishing the exam. Remember, some questions may be asked twice in different ways in the exam. If you request for regrading later, you must use ink pen to answer your exam. Good luck. I. II. III. IV. V. __________________ / 90 pts (multiple choice) __________________ / 80 pts (single step reactions) __________________ / 50 pts (mechanisms and short answers) __________________ / 40 pts (multiple step synthesis) __________________/ 40 + 10 pts (structures + bonus)

Total: __________________ / (300 + 10) pts

Part I. Multiple choice or simple questions (100 pts total)

Circle the letter corresponding to your best answer for each of the following questions. 1. (6 pts.) Predict the major product if the following reaction went by the SN1 pathway.
CH3COO-Na+ ?
Cl

OOCCH3 OOCCH3 OOCCH3

OOCCH3

(racemic) (A) (B) (C) (D) (E)

2.

(6 pts) Give the full IUPAC name for the following compound?
CH(CH3) 2

CH3

______________________________________ 3. (6pts) The greatest strength of infrared (IR) spectroscopy is in determining: (A). (B). (C). (D). (E). the degree of unsaturation. the relationship of structural fragments. the functional groups present. the exact structure of the molecule. if rings are present.

4. (6 pts) Which of the following reagents might serve as the basis for a simple test that would distinguish between pure cyclohexene and cyclohexane? (A) Br2/CCl4 (B) (C) (D) (E) dilute KMnO4/NaOH none of (A) and (B) both of (A) and (B) dilute NaOH/H2O
2

5. (6 pts) A compound with the molecular formula C3H6Cl2 gave a proton NMR spectrum consisting of a triplet (3) centered at 3.7 and a quintet (5) centered at 2.2. What is the most likely structure for the compound? (A). (B). (C). (D). (E). CH3CH2CHCl2 CH3CHClCH2Cl ClCH2CH2CH2Cl CH3CCl2CH3 none of the above.

6. (6 pts) Which compound listed below would you expect to be the major product of the following E2 elimination reaction?
CH3 CH3CH2 C CH3 CH3 CH3CH2 C CH3 Br CH3 CH3CH2 C CH3 CH3 O C CH3 CH2 CH3 H 3C Br

CH3CH2ONa CH3CH2OH

CH3CH2 CH2

CH3 CH CH3 H 3C

CH(CH3) 2

(A)

(B)

(C)

(D)

(E)

7. (6 pts) What characteristics of alkynes would make it difficult to prepare cyclohexyne? (A). (B). (C). (D). (E). 8. the requirement for linearity at the triple bond carbons. the large electron density between carbons of a triple bond. the short carbon-carbon triple bond length. carbon-carbon triple bonds are more reactive than alkanes. all of these.

(6 pts) What major product is expected from the reaction shown below ?
excess HCl
CH 3C CH Cl CH3 CH2 CH Cl H 3C Cl C Cl CH3 CH3 H H

Cl CH3

Cl H

Cl

Cl

Cl

CH3 CH CH2

(A)

(B)

(C)
3

(D)

(E)

9.

(6 pts) What is the relationship between alcohols I and II below? (A). (B). (C). (D). (E). different conformations of the same compounds (conformers). constitutional isomers. enantiomers. diastereomers. identical.
H H CH3 OH H H CH3

(I)

(II)

OH

10.

(6 pts) Which is the strongest nucleophile? (A). (B). (C). (D). (E). OH CH3CH2OH CH3CH2O CH3COO H2O

11.

(6 pts) Markovnikov addition of HCl to propene involves: (A). (B). (C). (D). (E). initial attack by a chloride ion. initial attack by a chlorine atom. isomerization of 1-chloropropane. formation of a 1-propyl cation (CH3CH2CH2+) formation of an isopropyl cation ( (CH3)2CH+ )

12. (6 pts). Which of the following would be a reasonable synthesis of CH3CH2CH2CH2OH?

(A). (B). 1-butene 1-butene H3O+, H2 O, heat 1). BH3:THF 2). H2O2, NaOH (C). 1-butene 1). Hg(OAc)2 /H2O 2). NaBH4

(D). (E).

more than one of these. none of these.

13.
(A)

(6 pts) Which reaction is NOT stereospecific?

H H 3C H

+ CH3 CO3H
CH3 O

H 3C

H CH3

(B)
H

+ Br2

(C)

H H 3C

CH3 H

+ OH

(D)

H 3C CH2 CH3 H 2C

H2 Pt

(E).

KMnO4, NaOH 5 oC

14.

(6 pts). Which ion is the weakest base? (A). (B). (C). (D) (E) CH3CH2CH2=CHHCCHOH2N-

15.

(6 pts). The correct IUPAC name for the following compound is:
H 3C C Br C CH2 CH CH3 Cl CH3

(A). (B). (C). (D). (E).

(E)-2-bromo-3-chloro-5-methyl-2-hexene. (E)-2-bromo-3-chloro-5-methyl-3-hexene (Z)-2-bromo-3-chloro-5-methyl-2-hexene. (Z)-2-bromo-3-chloro-5-methyl-3-hexene. (Z)-2-methyl-5-bromo-4-chloro-4-hexene

Part II. (80 pts) single step reactions

Complete the following questions, by providing the product(s), reagents, or reactants in the appropriate boxes. Assume aqueous work up has been performed. Pay attention to stereochemistry where necessary. 16 (10 pts).
Br CH3

Br2 H2O

H CH3 OH

17 (10 pts) .

H C CH2

CH2 CH2 OH

18 (10 pts) .

OsO4 H2O2

19 (10 pts) .

1). NaNH2
CH3 C CH

2). CH3 C CH3

O

20 (10 pts).

CH3

SOCl2

OH

21 (10 pts).

MgBr

+ H2 C=O

22 (10 pts).

(CH3 )3C CH Br

CH3

EtOH/H2O E1 reaction

23 (10 pts).

CH3CH2 CH Br

CH2 Br

CH3CH2 C

CH

Part III.

(50 pts) Mechanism and short answers

24. (15 pts) 1,2-diols may undergo rearrangements in acid-catalyzed reactions. Propose a mechanism for the following reaction to account for the formation of both products.
H2SO4
H 3C OH OH CH3 O CH3 CH3

+
H 3C O CH3

25. (15 pts). Explain why the following deuterated 1-bromo-2-methylcyclohexane undergoes dehydrohalogenation by the E2 mechanism, to give only the indicated product, but two other alkenes are not observed.
H CH3 Br D H H H H H CH3 H D CH3 H D H CH3

CH3O Na

observed

not observed.

26. (10 pts). What is the percent composition of a mixture of (S)-(+)-2-butanol, []D = +13.52o, and (R)-(-)-2-butanol, []D = -13.52o, with a specific rotation []D = +6.76o?

27. (10 pts). Draw the potential energy curve for the rotation of butane about its C2C3 single bond. Show Newman projection formulas for the energy maxima and minima. You do not need to specify the exact energy values, but you should pay attention to the relative energies of different conformers.

180 dihedral angle

360

Part IV (40 points). Multiple step synthesis Propose a synthesis for the following target molecules, starting from the compound(s) specified. You may use any inorganic reagents or organic compounds with two (2) or less carbon atoms. 28. (15 pts).
CH3CH2 CH3CH2 C CH H

....
H CH2 CH3

29.

(10 pts).

CH3 CH OH CH3

CH3

and

....
CH3

CH CH2 CH2 OH

30. (15 pts).

OH

....
OH

10

Part IV (40 points). Structure and Identification of unknowns 31. (20 pts) Reaction of (Z)-2-butene and Bromine yields a mixture of 2 compounds.
CH3

Br2 CCl4

Br

H CH3

Br CH3

CH3

H Br

CH3

Br H

CH3

(X)

(Y)

(a). (1 pts). Are compounds (X) and (Y) above formed in equal amount? ________ (b). (2 pts). What is this mixture called? _______________________

(c). (2 pts). Is a solution of the reaction mixture (X) and (Y) optically active? _______ (d). (1 pts). How many stereocenters are there in compound (X)? ___________ (e). (2 pts). Use a star (*) to indicate the stereocenters of compound (X) below:
Br H CH3

H Br

CH3

(X)

(f). (4 pts). Assign the appropriate R or S label to each of the stereocenters above. (g). (2 pts). What is the relationship between compounds (X) and (Y) (Use the proper stereochemistry term, NOT symmetry operations). _____________________ Reaction of (E)-2-butene and Bromine yields a single compound (Z):
H 3C H 3C H Br

Br2 CCl4
Br H

CH3

CH3

(Z)

(h). (1 pt). How many stereocenters are there in compound (Z)? _______________ (i). (1 pts). Is compound (Z) optically active? ________________

(j). (2 pts). What stereochemical term is used to describe compound (Z)? ___________ (k). (2 pts). What is the stereo relationship between (X) and (Z)? ______________

11

32. (10 pts). Compound, W, has the molecular formula C7H12. On catalytic hydrogenation, 1 mole of C absorbs 1 mole of hydrogen and yields a compound with the molecular formula C7H14. On ozonolysis and subsequent treatment with (CH3)2S, it yields only:
O O H 3C C H

What is the structure of compound W? (As usual, you must provide explanations).

33 (10 points). Propose a structure for the compound whose proton NMR is shown. You must show your work to receive credits. (the peaks at 1.2 are triplet, and 2.6 is quartet).

C8H10

12

Bonus (10 points). Propose a structure for the compound whose proton NMR is shown. You must show your work to account for each NMR peak to receive credits.

C3H6Cl2

13